Tunable structural rearrangement in Cu cluster assemblies through linker and solvent alterations

Abstract

The scarcity of approaches to assembling copper nanoclusters (Cu NCs) has restricted advancements in Cu NCs research, largely due to stability challenges of the individual NCs. By utilizing the structural adaptability of Cu NCs, we systematically investigate how variations in organic linkers and solvents affect the cluster node size, shape, and their assembling dimensionality. Here, we introduce a facile, one-pot synthesis method for obtaining a range of crystalline Cu cluster-assembled materials (CAMs) through a liquid-liquid interfacial crystallization technique. Our approach demonstrates that the electronic environment of linker molecules plays a crucial role in constructing the geometry of cluster nodes and the overall dimensionality of the framework. Solvent effects further influence the electronic environment of linkers, leading to tunable rearrangements in cluster node size and geometry. Additionally, coordination sites of the linker molecules and architectural properties significantly affect the overall dimensionality of the frameworks. Furthermore, correlations between solid-state photophysical properties and structural architecture expand the scope of this study, introducing the potential for tunable optical properties. We anticipate that this work will not only open avenues for designing novel Cu CAMs but also guide future research toward Cu-based materials with customizable optical features.